Cross-Coupling Reactions Involving Metal Carbene Migratory Insertion

Transcription

1 Cross-Coupling Reactions Involving Metal Carbene Migratory Insertion (Report of PhD Work in Prof. Jianbo Wang s group) Reporter:Ying Xia Supervisor: Prof. Guangbin Dong 11/11/2015 1

2 Generation of Metal Carbene and Their Classic Reactions For reviews, see: (a) Zhang, Z.; Wang, J. Tetrahedron 2008, 64, (b) Davies, H. M. L.; Manning, J. R. Nature 2008, 451, 417. (c) Zhang, Y.; Wang, J. Eur. J. Org. Chem. 2011,

3 When Metal Carbene Process Meets Cross-Coupling Process Metal Carbene Process Cross-Coupling Process M = Pd For reviews, see: (a) Barluenga, J.; Valdés, C. Angew. Chem. Int. Ed. 2011, 50, (b) Shao, Z.; Zhang, H. Chem. Soc. Rev. 2012, 41, 560. (c) Xiao, Q.; Zhang, Y.; Wang, J. Acc. Chem. Res. 2013, 46,

4 Content 1. Carbene Reactions Involving Diazo Compounds or N- Tosylhydrazones 2. Carbene Cross-Coupling Reactions Involving Non-Diazo Compounds 3. Intramolecular Metal Carbene Dimerization and Beyond 4

5 Content 1. Carbene Cross-Coupling Reactions Involving Diazo Compounds or N-Tosylhydrazones From Pd, Cu Catalysis to Rh(I) Catalysis 5

6 Brief Introduction of Carbene Coupling Reactions The First Catalytic Carbene Coupling Reaction: Greenman, K. L.; Carter, D. S.; Van Vranken, D. L. Tetrahedron 2001, 57,

7 The Development of Pd, Cu Catalysis N-Tosylhydrazones (Good Precursors for Non-Stabilized Diazo Compounds) Barluenga, J.; Moriel, P.; Valdés, C.; Aznar, F. Angew. Chem. Int. Ed. 2007, 46, Oxidative Carbene Cross-Coupling Peng, C.; Wang, Y.; Wang, J. J. Am. Chem. Soc. 2008, 130, Cu(I)-Catalyzed Oxidative Carbene Cross-Coupling Xiao, Q.; Xia, Y.; Li, H.; Zhang, Y.; Wang, J. Angew. Chem. Int. Ed. 2011, 50,

8 Rh(I)-Catalyzed Carbene Cross-Coupling Tsoi, Y.-K.; Zhou, Z.; Yu, W.-Y. Org. Lett. 2011, 13,

9 Merging with C-C Activation of Benzocyclobutenols Prof. Murakami gave a report in Perking University on October 22 nd, Ishida, N.; Sawano, S.; Masuda, Y.; Murakami, M. J. Am. Chem. Soc. 2012, 134, Our Design: 9

10 Merging with C-C Activation of Benzocyclobutenols The first carbene insertion to C-C bond N 2 is the only byproduct (Highlighted by Synfacts, 2014, 10, 0508) Xia, Y.; Liu, Z.; Liu, Z.; Ge, R.; Ye, F.; Hossain, M.; Zhang, Y.; Wang, J. J. Am. Chem. Soc. 2014, 136, For DFT calculation, see: Wang, Y.; Wang, Y.; Zhang, W.; Zhu, Y.; Wei, D.; Tang, M.; Org. Biomol. Chem. 2015, 13,

11 Murakami s Asymmetric Carbene C-C Bond Insertion Yada, A.; Fujita, S.; Murakami, M. J. Am. Chem. Soc. 2014, 136,

12 Merging with C-C Activation of VCP [5+2] Cycloaddition of VCP Wender, P. A.; Rieck, H.; Fuji, M. J. Am. Chem. Soc. 1998, 120, Our Design: [5+1] cycloaddition Initial Result: 12

13 Merging with C-C Activation of VCP Optimized Condition (By Sheng Feng) Selected Examples: (By Sheng Feng) Feng, S.; Xia, Y.; Mo, F.; Zhang, Y.; Wang, J. Unpublished result. 13

14 C-C Activation of Simple tert-alcohol Xia, Y; Liu, Z.; Liu, Z.; Ge, R.; Ye, F.; Hossain, M.; Zhang, Y.; Wang, J. J. Am. Chem. Soc. 2014, 136, 3013.

15 Three-Component Reaction with Propargyl Alcohols and Alkyl Halides Two C-C Bonds Formation Four Different Carbon Substituents on Quaternary Carbon Xia, Y.; Feng, S.; Liu, Z.; Zhang, Y.; Wang, J. Angew. Chem. Int. Ed. 2015, 54, (Hot Paper) 15

16 The Effect of Propargyl Alcohols 16

17 Selected Examples 17

18 Attempts to Asymmetric Synthesis Asymmetric Catalysis Asymmetric Induction 18

19 Reaction with Propargyl Alcohols and Internal Alkyl Halides Design: Liu, Z.; Xia, Y.*; Feng, S.; Zhang, Y.; Wang, J.* To be submitted. 19

20 Hiyama-Type Coupling with Aryl Silicon Regents 20

21 Hiyama-Type Coupling with Aryl Silicon Regents Xia, Y.; Liu, Z.; Feng, S.; Ye, F.; Zhang, Y.; Wang, J. Org. Lett. 2015, 17,

22 Hiyama-Type Coupling with Aryl Silicon Regents Xia, Y.; Liu, Z.; Feng, S.; Ye, F.; Zhang, Y.; Wang, J. Org. Lett. 2015, 17,

23 Hiyama-Type Coupling with Aryl Silicon Regents (a) Diazo Competetion:electron-rich diazoester expressed a higher reaction rate (b) Arylsiloxane Competetion:electron-deficient arylsiloxane expressed a higher reaction rate 23

24 Hiyama-Type Coupling with Aryl Silicon Regents 24

25 Stille-Type Coupling with Aryl Tin Regents Finished by Zhen Liu Liu, Z.; Xia, Y.*; Feng, S.; Wang, S.; Qiu, D.; Zhang, Y.; Wang, J.* Aust. J. Chem. 2015, 68,

26 Other TM-Catalyzed Carbene Coupling Reaction-Pd Reductive Coupling C(sp 3 )-C(sp 2 ) Bond Formation The Effect of CH 3 CO 2 NH 4 Xia, Y.; Hu, F.; Liu, Z.; Qu, P.; Ge, R.; Zhang, Y.; Wang, J. Org. Lett. 2013, 15, (Highlighted by organic-chemistry.org) 26

27 Other TM-Catalyzed Carbene Coupling Reaction-Pd Reductive Coupling C(sp 3 )-C(sp 2 ) Bond Formation Xia, Y.; Hu, F.; Liu, Z.; Qu, P.; Ge, R.; Zhang, Y.; Wang, J. Org. Lett. 2013, 15, (Highlighted by organic-chemistry.org) 27

28 Other TM-Catalyzed Carbene Coupling Reaction-Ir Xia, Y.; Liu, Z.; Feng, S.; Zhang, Y.; Wang, J. J. Org. Chem. 2015, 80,

29 Content 1. Carbene Cross-Coupling Reactions Involving Diazo Compounds or N-Tosylhydrazones From Pd, Cu Catalysis to Rh(I) Catalysis 29

30 Content 2. Carbene Cross-Coupling Reactions Involving Non-Diazo Compounds 30

31 Conjugated Enynone Used as Carbene Precursor Carbene Generation Conjugated Enynone) 31

32 Design of Carbene Coupling Reaction Using Conjugated Enynone Carbene Coupling Reaction Using Conjugated Enynone 32

33 Pd-Catalyzed Coupling Reaction of Enynones with Organo Halides Benzyl Bromides: Aryl Halides: Allylic Halides: Xia, Y.; Qu, S.; Xiao, Q.; Wang, Z.-X.; Qu, P.; Chen, L.; Liu, Z.; Tian, L.; Huang, Z.; Zhang, Y.; Wang, J. J. Am. Chem. Soc. 2013, 135, (Contributed Equally) (Highlighted by ChemCatChem 2014, 6, 711) 33

34 Proposed Mechanism Xia, Y.; Qu, S.; Xiao, Q.; Wang, Z.-X.*; Qu, P.; Chen, L.; Liu, Z.; Tian, L.; Huang, Z.; Zhang, Y.; Wang, J.* J. Am. Chem. Soc. 2013, 135, (Contributed Equally) (Highlighted by ChemCatChem 2014, 6, 711) 34

35 Pd-Catalyzed Oxidative Coupling of Enynones with Organoboronic Acid Strange E/Z Selectivity Xia, Y.; Ge, R.; Chen, L.; Liu, Z.; Xiao, Q.; Zhang, Y.; Wang, J. J. Org. Chem. 2015, 80,

36 Pd-Catalyzed Oxidative Coupling of Enynones with Terminal Alkynes Xia, Y.; Liu, Z.; Ge, R.; Xiao, Q.; Zhang, Y.; Wang, J. Chem. Commun. 2015, 51,

37 Rh(I)-Catalyzed Coupling of Enynones with Organoboronic Acids Xia, Y.; Chen, L.; Qu, P.; Ji, G.; Xiao, Q.; Zhang, Y.; Wang, J.To be submitted. 37

38 Proposed Mechanism 38

39 Carbene Coupling Reaction Involving Conjugated Allenyl Ketones Carbene Generation from Allenyl Ketone For review, see: Gulevich, A. V.; Dudnik, A. S.; Chernyak, N.; Gevorgyan, V. Chem. Rev. 2013, 113, Allenyl Ketone Involved Carbene Coupling Reaction Xia, Y.; Xia, Y; Ge, R.; Liu, Z.; Xiao, Q.; Zhang, Y.; Wang, J. Angew. Chem. Int. Ed. 2014, 53,

40 Summary of Carbene Coupling Reaction Using Non-Diazo Precursors Xia, Y.; Xia, Y; Ge, R.; Liu, Z.; Xiao, Q.; Zhang, Y.; Wang, J. Angew. Chem. Int. Ed. 2014, 53,

41 Content 3. Intramolecular Metal Carbene Dimerization and Beyond Construction Of Polycyclic Aromatic Compounds (PACs) 41

42 Brief Introduction of Carbene Dimerization Widely Exist in Carbene Involved Reactions (Controllability, Selectivity) Intramolecular Doyle, M. P.; Hu, W.; Phillips, I. M. Org. Lett. 2000, 2, 1777 Intermolecular Hansen, J. H.; Parr, B. T.; Pelphrey, P.; Jin, Q.; Autschbach, J.; Davies, H. M. L. Angew. Chem. Int. Ed. 2011, 50,

43 Application of Polycyclic Aromatic Compounds (PACs) Polycyclic Aromatic Hydrocarbons; Harvey, R. G., Eds.; Wiley-VCH: New York, N. Y., Alkali-metal-doped picene can show superconductivity (T c = 18 K), and this is the first example of organic superconducting material. Mitsuhashi, R.; Suzuki, Y.; Yamanari, Y.; Mitamura, H.; Kambe, T.; Ikeda, N.; Okamoto, H.; Fujiwara, A.; Yamaji, M.; Kawasaki, N.; Maniwa, Y.; Kubozono, Y. Nature 2010, 464,

44 Design for Construction Of PACs

45 Construction of PACs via Carbene Dimerization Xia, Y.; Liu, Z.; Xiao, Q.; Qu, P.; Ge, R.; Zhang, Y.; Wang, J. Angew. Chem. Int. Ed. 2012, 51, (Highlighted by ACS Noteworthy Chemistry) 45

46 Applications of Carbene Dimerization Methodology Our Method: Previous Method: Okamoto, H. et al, Org. Lett. 2011, 13,

47 Applications of Carbene Dimerization Methodology A concise synthesis of furostifoline 6 steps, overall yield 42.7% 47

48 Unexpected Result Optimized Conditions: 48

49 Substrate Scope: Migratory Group Investigation Xia, Y.; Qu, P.; Liu, Z.; Ge, R.; Xiao, Q.; Zhang, Y.; Wang, J. Angew. Chem. Int. Ed. 2013, 52, (Highlighted by Synfacts 2013, 9, 0492.) 49

50 Substrate Scope: Substituted Phenanthrenes 50

51 Substrate Scope: α-naphthol 51

52 Substrate Scope: β-naphthol 52

53 Application: Further Transformation Xia, Y.; Qu, P.; Liu, Z.; Ge, R.; Xiao, Q.; Zhang, Y.; Wang, J. Angew. Chem. Int. Ed. 2013, 52, (Highlighted by Synfacts 2013, 9, 0492.) 53

54 Application: Synthesis of DBC Derivatives 54

55 Summary of Carbene Dimerization 55

56 Conclusion and Outlook Intermolecular Couplings of Metal Carbene C-C Bond Formation Intramolecular Couplings of Metal Carbene C=C Bond Formation 56

57 Thank you for your attention! 57

58 Rationalization of diastereoselectivity: 58

59 Proposed Mechanism: 59

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